Photosensitive resin composition, electronic component using the same, and display using same

ABSTRACT

This invention relates to a negative-working photosensitive resin composition that can be developed in an alkaline developer. This photosensitive resin composition comprises: (a) a polyimide having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group at the terminus of the polymer main chain; (b) a compound having a polymerizable functional group comprising unsaturated double and/or triple bonds; and (c) a photopolymerization initiator.

TECHNICAL FIELD

The present invention relates to a heat resistant resin composition thatis suitable for a surface protective film of a semiconductor device, aninterlayer insulation film of a semiconductor device, an insulation filmof an organic electroluminescent element, and an insulation film forprotecting wirings of a circuit board. More particularly, the presentinvention relates to a negative-working photosensitive resincomposition, regarding which a portion that has not been exposed toultraviolet light is easily soluble in an aqueous alkaline solution anda portion that has been exposed to such ultraviolet light is insolublein such solution, an electronic component using the same, and a displayunit using the same.

BACKGROUND ART

In the semiconductor industry, inorganic materials have been heretoforeused as interlayer insulation films. In recent years, resin compositionshaving excellent heat resistance, such as polyimide or polybenzoxazole,have been used as interlayer insulation films because of theirproperties. However, the formation of patterns on the semiconductorintegrated circuits or the printed circuit board involves complicatedand extensive processes, such as formation of a film of a resistmaterial on the surface of the substrate, exposure of a given site,removal of unnecessary sites via etching or the like, and washing of thesurface of the substrate. Accordingly, a heat resistant photosensitivematerial was developed, via which a resist material at a portion that isnecessary after pattern formation via exposure and developing can bemaintained and used as an insulation material.

Heat resistant photosensitive materials, such as photosensitivepolyimide and photosensitive polybenzoxazole, have been developed andput to practical use. Negative-working photosensitive polyimidematerials that employ organic solvents in developing have excellent heatresistance, and impurities can be easily removed therefrom. Accordingly,such negative-working photosensitive polyimide materials are employed bya large number of device manufacturers. Such negative-workingphotosensitive polyimide materials, which are produced by a method (JPPatent Publication (Unexamined) Nos. 54-109828 (1979) and 11-24268(1999)), wherein a compound having a photosensitive group is added to ormixed with a polyimide precursor, develop contrast via crosslinking andthe like to form patterns. These negative-working photosensitivepolyimide materials are basically designed to be suitable for developingthat employs organic solvents. However, these materials are not intendedto cope with developing that employs an aqueous alkaline solution (i.e.,an aqueous solution of tetramethylammonium hydroxide), which isconsidered to be less problematic in terms of waste liquid processing inview of the environmental consciousness of recent years, and they havepoor solubility. Thus, it was difficult for them to form patterns.Further, negative-working photosensitive polyimide materials that canemploy an alkaline solution in developing must comprise analkali-soluble group as base material. In contrast, it was difficult toefficiently reproduce patterns following efficient developing with theuse of a negative-working and alkaline-developable photosensitivepolyimide precursor, which is prepared by a method wherein aphotoreactive group is introduced into some of the alkali-soluble groupsof the polyimide precursor (EP 0421195, JP Patent Publication(Unexamined) No. 2002-182378), because of deteriorated polymersolubility in an alkaline developer caused by the introduction of aphotoreactive group. Even if patterns were effectively reproducedfollowing developing, film is significantly cured and shrunk upon thering closure reaction that occurs when a polyimide precursor is finallyconverted into a polyimide. When a thick film of 20 μm or more was used,the film became cracked and thus was difficult to use. Although apolyimide that was soluble in an organic solvent and in alkali wasdeveloped, it was difficult to efficiently reproduce good patternsfollowing developing when a photoreactive group was introduced into someof the alkali-soluble groups of the polymer. Thus, a photo acidgenerator or a photo acid generator and an acid crosslinking agent areadded to the composition instead of introducing a photoreactive group tothe polymer to prepare a positive-working or negative-working material(EP 1199604 and JP Patent Publication (No.) 10-316751 (1998)).

DISCLOSURE OF THE INVENTION

The present invention provides a negative-working photosensitive resincomposition, regarding which a portion that has not been exposed toultraviolet light is easily soluble in an aqueous alkaline solution anda portion that has been exposed to such ultraviolet light is insolublein such solution, using an alkali-soluble and organic solvent-solublepolyimide having a specific structure. The present invention alsoprovides a composition that renders the aforementioned polyimide easilysoluble in an alkaline developer before exposure and insoluble thereinafter exposure, thereby effectively reproducing fine patterns.

More specifically, the present invention relates to a photosensitiveresin composition comprising: (a) a polyimide having at least one groupselected from the group consisting of a carboxyl group, a phenolichydroxyl group, a sulfonic acid group, and a thiol group at the terminusof the polymer main chain; (b) a compound having a polymerizablefunctional group comprising unsaturated double and/or triple bonds; and(c) a photopolymerization initiator.

The present invention can provide a polyimide having an alkali-solublegroup at its polymer terminus and being soluble in an alkaline solutionas well as in an organic solvent via adequate regulation of polymermolecular weight. Use thereof as a base polymer can eliminate the needfor imide conversion of a polymer via high-temperature-treatment afterdeveloping with an aqueous alkaline solution. Also, a negative-workingphotosensitive resin composition can be obtained, which is excellent inpattern formation, heat shrinkability, crack resistance, stressresistance, and practicability in heat treatment. The resultingcomposition is particularly preferably used for a surface protectivefilm of a semiconductor device, an interlayer insulation film of asemiconductor device, an insulation film of a display unit, and aninsulation film for protecting wirings of a circuit board.

This description includes part or all of the contents as disclosed inthe description and/or drawings of Japanese Patent Application No.2003-156269, which is a priority document of the present application.

PREFERRED EMBODIMENT OF THE INVENTION

In terms of usefulness, the polyimide used in the present invention issoluble not only in an organic solvent but also in an alkaline solutionbecause it has an alkali-soluble group at the terminus of its polymermain chain. Because of the polyimide structure, it is not necessary toprepare an imide ring via a ring closure reaction via heating or withthe aid of an adequate catalyst, unlike the case of a polyimideprecursor. Accordingly, high temperature treatment is unnecessary,stress resulting from curing and shrinkage via imide ring closure issmall, and thus, a thick film can be formed more easily than with theuse of a polyimide precursor. In view of practicability concerning analkaline developer used in the semiconductor industry, an alkali-solublegroup used in the polyimide of the present invention is preferably ahydroxyl group (particularly a phenolic hydroxyl group), a thiol group,or a carboxyl group. A phenolic hydroxyl group and a thiol group areparticularly preferable.

In the present invention, a resin composition is obtained by adding acompound having a polymerizable functional group comprising unsaturateddouble and/or triple bonds and a photopolymerization initiator to apolyimide synthesized with the use of an endcap agent having analkali-soluble group. This composition is easily soluble in an alkalinedeveloper before exposure but becomes hardly soluble therein afterexposure. Thus, a reduction in film thickness caused by developing issmall, and imide conversion of a polymer via high-heat treatmentfollowing developing with an aqueous alkaline solution is not necessary.Thus, the composition of the present invention is excellent in patternformation, heat shrinkability, crack resistance, stress resistance, andpracticability in heat treatment (low-temperature treatment).

In these formulae, R¹ represents a 4- to 14-valent organic group; R²represents a 2- to 12-valent organic group; R³ and R⁵ each represent ahydrogen atom or an organic group having at least one member selectedfrom the group consisting of a phenolic hydroxyl group, a sulfonic acidgroup, a thiol group, and organic groups having 1 to 20 carbon atoms,which may be the same or different; R⁴ represents a 2-valent organicgroup; X and Y each represent a 2-valent to 8-valent organic grouphaving at least one member selected from the group consisting of acarboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and athiol group; n is a number between 3 and 200; and m, α, and β are eachan integer between 0 and 10.

In formulae (1) to (4), R¹ represents structural elements of aciddianhydrides, which are 4- to 14-valent organic groups comprisingaromatic or aliphatic rings. Organic groups having 5 to 40 carbon atomsare particularly preferable.

Specific examples of acid dianhydrides include: aromatic tetracarboxylicacid dianhydrides, such as pyromellitic acid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride,2,3,3′,4′-biphenyltetracarboxylic acid dianhydride,2,2′,3,3′-biphenyltetracarboxylic acid dianhydride,3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride,2,2′,3,3′-benzophenonetetracarboxylic acid dianhydride,2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,bis(3,4-dicarboxyphenyl)methane dianhydride,bis(2,3-dicarboxyphenyl)methane dianhydride,bis(3,4-dicarboxyphenyl)sulfone dianhydride,bis(3,4-dicarboxyphenyl)ether dianhydride,1,2,5,6-naphthalenetetracarboxylic acid dianhydride,9,9-bis(3,4-dicarboxyphenyl)fluorene acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene acid dianhydride,2,3,6,7-naphthalenetetracarboxylic acid dianhydride,2,3,5,6-pyridinetetracarboxylic acid dianhydride,3,4,9,10-perylenetetracarboxylic acid dianhydride, and2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; aliphatictetracarboxylic acid dianhydrides, such as butanetetracarboxylic aciddianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride;3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride; and an aciddianhydride having the structure shown below.

In the formula, R⁷ represents an oxygen atom or a group selected fromthe group consisting of C(CF₃)₂, C(CH₃)₂, and SO₂; and R⁸ and R⁹ may bethe same or different and each represent a group selected from the groupconsisting of a hydrogen atom, a hydroxyl group, and a thiol group.

Among these compounds, 3,3′,4,4′-biphenyltetracarboxylic aciddianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride,2,2′,3,3′-biphenyltetracarboxylic acid dianhydride,3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride,2,2′,3,3′-benzophenonetetracarboxylic acid dianhydride,2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,bis(3,4-dicarboxyphenyl)methane dianhydride,bis(2,3-dicarboxyphenyl)methane dianhydride,bis(3,4-dicarboxyphenyl)sulfone dianhydride,bis(3,4-dicarboxyphenyl)ether dianhydride,2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride,3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride,9,9-bis(3,4-dicarboxyphenyl)fluorene acid dianhydride,9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene acid dianhydride, and anacid dianhydride having the structure shown below are preferable. Thesecompounds may be used alone or in combinations of two or more.

In the formula, R⁷ represents an oxygen atom or a group selected fromthe group consisting of C(CF₃)₂, C(CH₃)₂, and SO₂; and R⁸ and R⁹ may bethe same or different and each represent a group selected from the groupconsisting of a hydrogen atom, a hydroxyl group, and a thiol group.

In formulae (I) to (4), R² represents structural elements of diamine,which are 2-valent to 12-valent organic groups comprising aromatic oraliphatic rings. Organic groups having 5 to 40 carbon atoms areparticularly preferable.

Specific examples of diamine include 3,4′-diaminodiphenyl ether,4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane,4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenyl sulfone,4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfide,4,4′-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine,m-phenylenediamine, P-phenylenediamine, 1,5-naphthalenediamine,2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone,bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene,2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl,3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl,2,2′,3,3′-tetramethyl-4,4′-diaminobiphenyl,3,3′,4,4′-tetramethyl-4,4′-diaminobiphenyl,2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl,9,9-bis(4-aminophenyl)fluorene, compounds obtained by substituting oneor more hydrogens of aromatic rings of these substances with alkylgroups or halogen atoms; aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamine having the structure shown below:

wherein R⁷ represents an oxygen atom or a group selected from the groupconsisting of C(CF₃)₂, C(CH₃)₂, and SO₂; and R⁸ to R¹¹ may be the sameor different and each represent a group selected from the groupconsisting of a hydrogen atom, a hydroxyl group, and a thiol group.

Among these compounds, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone,3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide,m-phenylenediamine, P-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene,9,9-bis(4-aminophenyl)fluorene, and diamine having the structure shownbelow are preferable:

wherein R⁷ represents an oxygen atom or a group selected from the groupconsisting of C(CF₃)₂, C(CH₃)₂, and SO₂; and R⁸ to R¹¹ may be the sameor different and each represent a group selected from the groupconsisting of a hydrogen atom, a hydroxyl group, and a thiol group.3,4′-Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether,3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone,1,4-bis(4-aminophenoxy)benzene, and diamine having the structure shownbelow are particularly preferable. These compounds may be used alone orin combinations of two or more.

In the formula, R⁷ represents an oxygen atom or a group selected fromthe group consisting of C(CF₃)₂, C(CH₃)₂, and SO₂; and R⁸ and R⁹ may bethe same or different and each represent a group selected from the groupconsisting of a hydrogen atom, a hydroxyl group, and a thiol group.

In formulae (1) to (4), R³ and R⁵ each represent a hydrogen atom, aphenolic hydroxyl group, a sulfonic acid group, a thiol group, or anorganic group having 1 to 20 carbon atoms. From the viewpoint ofstability of the resulting solution of photosensitive resin composition,R³ and R⁵ each preferably represent a hydrogen atom or an organic group.From the viewpoint of solubility in an aqueous alkaline solution, analkali-soluble group, i.e., a phenolic hydroxyl group, a sulfonic acidgroup, or a thiol group, is preferable.

In the present invention, a phenolic hydroxyl group, a sulfonic acidgroup, or a thiol group and a hydrogen atom or an alkyl group may existsimultaneously.

By regulating the amounts of an alkali-soluble group, hydrogen, or anorganic group represented by R³ and R⁵, the rate of dissolution in anaqueous alkaline solution can be altered. Thus, a negative-workingphotosensitive resin composition having a more adequate rate ofdissolution can be obtained. Preferably, the abundance of analkali-soluble group in R³ and in R⁵ is 5% to 100% thereof. When anorganic group represented by R³ or R⁵ has more than 20 carbon atoms, thecomposition becomes insoluble in an aqueous alkaline solution.Accordingly, R³ and R⁵ each preferably comprise a hydrogen atom or atleast one hydrocarbon group having 1 to 16 carbon atoms and the balanceis an alkali-soluble group.

NH—(R⁴)m-X, which is a constituent of formulae (1) and (2), ispreferably represented by formula (6), which is a component derived froma primary monoamine as an endcap agent. X is preferably a 2-valent to8-valent organic group having at least one member selected from thegroup consisting of a carboxyl group, a phenolic hydroxyl group, asulfonic acid group, and a thiol group, and more preferably a 2-valentto 8-valent organic group having at least one member selected from thegroup consisting of a carboxyl group, a phenolic hydroxyl group, and athiol group.

—CO—(R⁴)m-Y, which is a constituent of formulae (3) and (4), ispreferably represented by formulae (7) and (8), which is a componentderived from a substance selected from the group consisting of an acidanhydride, a monocarboxylic acid, a monoacid chloride compound, or amonoactivated ester compound, as an endcap agent. Y is preferably a2-valent to 8-valent organic group having at least one member selectedfrom the group consisting of a carboxyl group, a phenolic hydroxylgroup, a sulfonic acid group, and a thiol group. More preferably, Y is a2-valent to 8-valent organic group having at least one member selectedfrom the group consisting of a carboxyl group, a phenolic hydroxylgroup, and a thiol group. In formulae (3) and (4), Y may include only anendcap group represented by formula (7), only an endcap grouprepresented by formula (8), or both groups represented by formulae (7)and (8).

In formulae (6) to (8), R⁴ represents a 2-valent group selected from thegroup consisting of —CR¹⁷R¹⁸—, —CH₂O—, and —CH₂SO₂—; and R¹⁷ and R¹⁸each represent a monovalent group selected from the group consisting ofa hydrogen atom, a hydroxyl group, and hydrocarbon groups having 1 to 10carbon atoms; and R¹⁴ represents a monovalent group selected from thegroup consisting of a hydrogen atom and hydrocarbon groups having 1 to10 carbon atoms. A hydrogen atom or hydrocarbon groups having 1 to 4carbon atoms is preferable, and a hydrogen atom, a methyl group, and at-butyl group are particularly preferable. R¹⁵ and R¹⁶ each represent amonovalent group selected from the group consisting of a hydrogen atomand hydrocarbon groups having 1 to 4 carbon atoms or a ring structurewherein R¹⁵ is directly bound to R¹⁶ (e.g., a nadiimide ring). R¹² andR¹³ are each selected from the group consisting of a hydrogen atom, ahydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group,and hydrocarbon groups having 1 to 10 carbon atoms. At least one of R¹²and R¹³ is a hydroxyl group, a carboxyl group, a sulfonic acid group, ora thiol group. A, E, and G are carbon atoms or nitrogen atoms, which maybe the same or different. m is an integer between 0 and 10, andpreferably an integer between 0 and 4. 1 is 0 or 1, and preferably 0. pis 0 or 1, and preferably 0. q is an integer between 1 and 3, andpreferably 1 or 2. r, s, and t are each 0 or 1.

In formula (6), specific examples of the primary monoamines include5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline,1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene,1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene,1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene,1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene,2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene,2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene,2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene,1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene,1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene,1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene,1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene,2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene,2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene,2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene,2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid,6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid,6-aminosalicylic acid, 3-amino-o-toluic acid, ammelide, 2-aminobenzoicacid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonicacid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid,3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol,4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline,1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene,1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene,1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene,1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene,2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene,2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene,2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene,3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol,and 4-aminothiophenol.

Among these compounds, for example, 5-amino-8-hydroxyquinoline,1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene,1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene,2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene,2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene,1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene,2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene,2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid,4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid,6-aminosalicylic acid, 2-aminobenzenesulfonic acid,3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid,3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol,4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and4-aminothiophenol are particularly preferable. They may be used alone orin combinations of two or more.

In formulae (7) and (8), specific examples of the acid anhydride, themonocarboxylic acid, the monoacid chloride compound, and themonoactivated ester compound include: acid anhydrides, such as phthalicanhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylicanhydride, and 3-hydroxyphthalic anhydride; monocarboxylic acids, suchas 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol,2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol,1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene,1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene,1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene,1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene,1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene,1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene,1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene,2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid,4-carboxybenzenesulfonic acid, and monoacid chloride compounds of thesesubstances in which carboxylic groups thereof are chloridized; monoacidchloride compounds obtained by chloridizing monocarboxyl groups ofdicarboxylic acids such as terephthalic acid, phthalic acid, maleicacid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid,5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene,1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene,1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene,1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene,2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and2,7-dicarboxynaphthalene; and activated ester compounds obtained by thereaction between a monoacid chloride compound and N-hydroxybenzotriazoleor N-hydroxy-5-norbornene-2,3-dicarboxyimide.

Among these compounds, particularly preferred examples are: acidanhydrides, such as phthalic anhydride, maleic anhydride, nadic acid,cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride;monocarboxylic acids, such as 3-carboxyphenol, 4-carboxyphenol,3-carboxythiophenol, 4-carboxythiophenol,1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene,1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene,1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene,3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, andmonoacid chloride compounds of these substances in which carboxylicgroups thereof are chloridized; monoacid chloride compounds obtained bychloridizing monocarboxyl groups of dicarboxylic acids such asterephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylicacid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene,1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene; and activatedester compounds obtained by the reaction between a monoacid chloridecompound and N-hydroxybenzotriazole orN-hydroxy-5-norbornene-2,3-dicarboxyimide. They may be used alone or incombinations of two or more.

The amount of the introduced component represented by formula (6), i.e.,the component X in formulae (1) and (2), is preferably in the range of0.1 to 60 molar percent, and more preferably 5 to 50 molar percent,relative to the entire amine component when calculated based on theprimary monoamine component, which is the original component functioningas the endcap agent.

The amount of the introduced component represented by formulae (7) and(8), i.e., the component Y in formulae (3) and (4), is preferably in therange of 0.1 to 60 molar percent, and more preferably 5 to 55 molarpercent, relative to the diamine component when calculated based on theacid anhydride, the monocarboxylic acid, the monoacid chloride compound,or the monoactivated ester compound, which is the original componentfunctioning as the endcap agent.

In formulae (1) to (4), n represents the number of recurring structureunits of the polymer of the present invention, and n is preferably inthe range of 3 to 200, and more preferably in the range of 5 to 100.When n is smaller than 3, the viscosity of the composition may not beincreased, which may result in incapability of the use of thecomposition as a thick film. In contrast, when n is larger than 200, thecomposition may become insoluble in an alkaline developer.

When the structures represented by formulae (1) to (4) each contain 10%by weight or more of fluorine atoms, a suitable degree of waterrepellency is exhibited at the film interface during developing with anaqueous alkaline solution, thereby preventing leakage at the interface.At a content of fluorine atoms exceeding 20% by weight, however, thesolubility in an aqueous alkaline solution disadvantageously decreases.Thus, a content of fluorine atoms is preferably 10% to 20% by weight.

In order to enhance the adhesion to the substrate, R¹ and R² may becopolymerized with an aliphatic group having a siloxane structure aslong as the heat resistance is not deteriorated. Specific examplesthereof are those prepared by copolymerizing 1 to 10 molar percent ofbis(3-aminopropyl)tetramethyldisiloxane,bis(p-amino-phenyl)octamethylpentasiloxane, or the like, as the diaminecomponent.

The photosensitive resin composition of the present invention mayconsist of the structural units represented by formulae (1) to (4), orit may be copolymerized or mixed with other structural units. In such acase, the composition preferably comprises 50 molar percent or more ofthe structural units represented by formulae (1) to (4). The type andthe amount of the structural units to be copolymerized or mixed areadequately determined so as not to deteriorate the heat resistance ofthe polyimide polymer obtained by the final heat treatment.

The polyimide of the present invention is synthesized by a conventionalmethod whereby replaces part of a diamine with a monoamine endcap agentor whereby replaces the acid dianhydride with an endcap agent such as amonocarboxylic acid, an acid anhydride, a monoacid chloride compound, ora monoactivated ester compound. Examples of conventional methods thatcan be employed include: a method of allowing tetracarboxylicdianhydride to react with a diamine compound (part of which issubstituted by a monoamine endcap agent) at a low temperature; a methodof allowing tetracarboxylic dianhydride (part of which is substitutedwith an endcap agent, such as an acid anhydride, a monoacid chloridecompound, or a monoactivated ester compound) to react with a diaminecompound at a low temperature; a method comprising obtaining diesterfrom tetracarboxylic dianhydride and alcohol and allowing the diester toreact with diamine (part of which is substituted by a monoamine endcapagent) in the presence of a condensing agent; and a method comprisingobtaining diester from tetracarboxylic dianhydride and alcohol,chloridizing the remaining dicarboxylic acid, and allowing thechloridized dicarboxylic acid to react with diamine (part of which issubstituted with a monoamine endcap agent). Via such methods, apolyimide precursor is obtained and then converted to the complete imidevia a conventional technique of imide conversion. Alternatively, imideconversion is terminated in the middle of the reaction to introduce apartial imide structure. Further, a polymer of the complete imide ismixed with a polyimide precursor thereof to introduce a partial imidestructure.

The composition of the present invention preferably comprises polyimideto such an extent that the rate of imide conversion becomes 15% orhigher, and more preferably 20% or hither, based on the amount of thetotal polymer constituting the composition. The term “rate of imideconversion” used herein refers to the abundance of the imide compoundsin the entire polymer that constitutes the composition of the presentinvention. When the rate of imide conversion is lower than 15%, theshrinkage at the time of heat curing becomes enlarged, which isunsuitable for the formation of a thick film.

The rate of imide conversion can be easily calculated in the followingmanner. At the outset, the infrared absorption spectrum of the polymeris measured, and the absorption peaks of the polyimide imide structureare detected at around 1780 cm⁻¹ and 1377 cm⁻¹. Subsequently, thepolymer is subjected to heat treatment at 350° C. for 1 hour, theinfrared absorption spectrum is measured after heat treatment, and theobtained peak intensity at around 1377 cm⁻¹ is compared with theintensity before heat treatment to determine the rate of imideconversion in the polymer before heat treatment.

The composition of the present invention preferably comprises at leastone polyimide selected from resins having the structural unitsrepresented by formulae (1) to (4) as the component (a). In this case,such polyimide is preferably contained 10% by weight or more, and morepreferably 20% by weight or more, based on the amount of the entirepolymer that constitutes the composition of the present invention. Whensuch polyimide is contained 10% by weight or more based thereon, therate of imide conversion in the entire polymer constituting thecomposition is 15% or higher.

The endcap agent, which has been introduced into the polymer, can bereadily detected in the following manner. For example, the polymercontaining the endcap agent is dissolved in an acidic solution so as tobe decomposed into amine components and acid anhydride components, whichare the structure units of the polymer. Subsequently, gas chromatography(GC) or nuclear magnetic resonance (NMR) analysis is performed toreadily detect the endcap agent used in the present invention.Alternatively, the endcap agent can be readily detected by directlyperforming pyrolysis gas chromatography (PGC) or infrared spectrum andC13 NMR spectrum analysis on the polymer component containing the endcapagent.

A compound having the polymerizable group (b) that is used in thepresent invention comprises a polymerizable unsaturated functionalgroup. Examples of such functional group include an unsaturatedfunctional group comprising a double bond, such as a vinyl, allyl,acryloyl, or methacryloyl group, and/or an unsaturated functional groupcomprising a triple bond, such as a propargyl group. Among these groups,a conjugated vinyl, acryloyl, or methacryloyl group is particularlypreferable in terms of polymerizability. The number of the functionalgroups to be contained is preferably 1 to 4 from the viewpoint ofstability, and these groups may not be of the same type. The term“compound” used herein refers to a compound having a molecular weight of30 to 800.

Examples of compounds having polymerizable groups include diethyleneglycol diacrylate, triethylene glycol diacrylate, tetraethylene glycoldiacrylate, diethylene glycol dimethacrylate, triethylene glycoldimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropanediacrylate, trimethylolpropane triacrylate, trimethylolpropanedimethacrylate, trimethylolpropane trimethacrylate, styrene,α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene,3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate,butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctylacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexylmethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate,neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanedioldimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate,1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate,dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane,1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide,N,N-dimethylacrylamide, N-methylol acrylamide,2,2,6,6-tetramethylpiperidinyl methacrylate,2,2,6,6-tetramethylpiperidinyl acrylate,N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate,N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-vinyl pyrrolidone,and N-vinyl caprolactam. These compounds may be used alone or incombinations of two or more.

Among these compounds, particularly preferable compounds are, forexample, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate,dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornylmethacrylate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, pentaerythritol trimethacrylate, pentaerythritoltetramethacrylate, methylenebisacrylamide, N,N-dimethylacrylamide,N-methylol acrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate,2,2,6,6-tetramethylpiperidinyl acrylate,N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate,N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-vinyl pyrrolidone,and N-vinyl caprolactam.

In the present invention, the amount of the compound (b) to be used ispreferably 5 to 200 parts by weight based on 100 parts by weight of thepolymer (a). It is more preferably 5 to 150 parts by weight from theviewpoint of compatibility. When such amount is less than 5 parts byweight, the exposed area is dissolved at the time of developing. Thus, afilm may not remain after developing. When such amount exceeds 200 partsby weight, the film may not remain, either, and a film may becomewhitened at the time of film formation.

Examples of the photopolymerization initiators (c) used in the presentinvention include: benzophenones, such as benzophenone, Michler'sketone, 4,4,-bis(diethylamino)benzophenone, and3,3,4,4,-tetra(t-butylperoxycarbonyl)-benzophenone; benzylidenes, suchas 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone and3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone; coumarins, suchas 7-diethylamino-3-thenoylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin,3,3,-carbonylbis(7-diethylaminocoumarin),7-diethylamino-3-(1-methylbenzimidazoyl)coumarin, and3-(2-benzothiazolyl)-7-diethylaminocoumarin; anthraquinones, such as2-t-butylanthraquinone, 2-ethylanthraquinone, and 1,2-benzanthraquinone;benzoins, such as benzoinmethyl ether, benzoinethyl ether, andbenzoinisopropylether; thioxanthones, such as 2,4-dimethylthioxanthone,2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and2-isopropylthioxanthone; mercaptos, such as ethylene glycoldi(3-mercaptopropionate), 2-mercaptobenzothiazole,2-mercaptobenzoxazole, and 2-mercaptobenzimidazole; glycines, such asN-phenylglycine, N-methyl-N-phenylglycine,N-ethyl-N-(p-chlorophenyl)glycine, and N-(4-cyanophenyl)glycine; oximes,such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,bis(α-isonitrosopropiophenone oxime)isophthal, and 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime); α-aminoalkylphenones,such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one; and2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole. Among thesecompounds, oximes, such as1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,bis(α-isonitrosopropiophenone oxime)isophthal, and 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime) are preferable.1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,bis(α-isonitrosopropiophenone oxime)isophthal, and 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime) are particularlypreferable. These compounds may be used alone or in combinations of twoor more.

Among these compounds, a combination of the compound of the presentinvention with the aforementioned benzophenones, glycines, mercaptos,oximes, α-aminoalkylphenones, or2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole is preferablefrom the viewpoint of photoreaction. These photosensitizing agents maybe used alone or in combinations of two or more.

When a single type of photopolymerization initiator is used, the amountof the photopolymerization initiator (c) to be used is generally 0.1 to40 parts by weight based on 100 parts by weight of the polymer (a). Whentwo or more types of photopholymerization initiators are combined, atotal amount thereof is preferably 0.2 to 60 parts by weight.

Examples of the thermally crosslinkable compound (d) that is used in thepresent invention include a compound having a thermally crosslinkablegroup represented by formula (5) and a benzoxazine compound:

CH₂—OR⁶)  (5)wherein R⁶ represents a hydrogen atom, an alkyl group having 1 to 20carbon atoms, a alicyclic group having 4 to 20 carbon atoms, or an R⁷COgroup; and R⁷ represents an alkyl group having 1 to 20 carbon atoms.

Examples of the thermally crosslinkable compounds include: as thosehaving one of such a thermally crosslinkable group, ML-26×, ML-24×,ML-236TMP, 4-methylol3M6C, ML-MC, and ML-TBC (trade names, HonshuChemical Industry Co., Ltd.), and P-a type benzoxazine (trade name,Shikoku Chemicals Corp.); as those having two of such groups,DM-BI25X-F, 46DMOC, 46DMOIPP, and 46DMOEP (trade names, Asahi OrganicChemicals Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC,DML-PCHP, DML-PTBP, DML-34×, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C,dimethylol-Bis OC-P, DML-Bis OC-Z, DML-Bis OCHP-Z, DML-PFP, DML-PSBP,DML-MB25, DML-MTris PC, DML-Bis25X-34XL, and DML-Bis25X-PCHP (tradenames, Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name,Sanwa Chemical Co., Ltd.), B-a type benzoxazine and B-m type benzoxazine(trade names, Shikoku Chemicals Corp.),2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, and2,6-diacetoxymethyl-p-cresol; as those having three of such groups,TriML-P, TriML-35XL, and TriML-Tris Cr-HAP (trade names, Honshu ChemicalIndustry Co., Ltd.); as those having four of such groups, TM-BIP-A(trade name, Asahi Organic Chemicals Industry Co., Ltd.), TML-BP,TML-HQ, TML-pp-BPF, TML-BPA, and TMOM-BP (trade names, Honshu ChemicalIndustry Co., Ltd.), Nikalac MX-280 and Nikalac MX-270 (trade names,Sanwa Chemical Co., Ltd.); and as those having six of such groups,HML-TPPHBA and HML-TPHAP (trade names, Honshu Chemical Industry Co.,Ltd.) and Nikalac MW-390 and Nikalac MW-100LM (trade names, SanwaChemical Co., Ltd.).

Among these compounds, those including at least two thermallycrosslinkable groups are preferable in the present invention.Particularly preferable examples thereof include 46DMOC and 46DMOEP(trade names, Asahi Organic Chemicals Industry Co., Ltd.), DML-MBPC,DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34×, DML-EP,DML-POP, dimethylol-Bis OC-P, DML-PFP, DML-PSBP, and DML-MTris PC (tradenames, Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name,Sanwa Chemical Co., Ltd.), B-a type benzoxazine and B-m type benzoxazine(trade names, Shikoku Chemicals Corp.),2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, and2,6-diacetoxymethyl-p-cresol, TriML-P and TriML-35XL, (trade names,Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, Asahi OrganicChemicals Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, andTMOM-BP (trade names, Honshu Chemical Industry Co., Ltd.), NikalacMX-280 and Nikalac MX-270 (trade names, Sanwa Chemical Co., Ltd.), andHML-TPPHBA and HML-TPHAP (trade names, Honshu Chemical Industry Co.,Ltd.). Examples of more preferable compounds include alicycliccompounds, such as Nikalac MX-280 and Nikalac MX-270 (trade names, SanwaChemical Co., Ltd.), B-a type benzoxazine and B-m type benzoxazine(trade names, Shikoku Chemicals Corp.), and Nikalac MW-390 and NikalacMW-100LM (trade names, Sanwa Chemical Co., Ltd.).

The resin compounds obtained with the addition of such compounds (d)brings about thermally-induced crosslinking at the time of heattreatment, which further reduces the rate of shrinkage.

Among these thermally crosslinkable compounds (d), a compound having amethylol group or a substituted methylol group that is formed bysubstituting a hydrogen atom of an alcoholic hydroxyl group of amethylol group,₌ forms crosslinks by a reaction mechanism that bindsdirectly to benzene rings as shown below.

The structures of representative thermally crosslinkable compounds thatare particularly preferably used in the present invention are shownbelow:

The amount of such thermally crosslinkable compound to be added ispreferably 0.5 to 150 parts by weight, and more preferably 1 to 130parts by weight, based on 100 parts by weight of the polymer in thecomponent (a). When the amount of the thermally crosslinkable compound(d) to be added is larger than 150 parts by weight based on 100 parts byweight of the component (a), the resin content becomes too small, whichdeteriorates the heat resistance of the photosensitive resin film. Whensuch amount is smaller than 0.5 parts by weight, an increase in amolecular weight caused by crosslinking is small, which alsodeteriorates the heat resistance of the photosensitive resin film.

The colorant (e) used in the present invention blocks a stray light fromthe light-emitting area in the insulation film of the organicelectroluminescent element. Such colorant shields the circuit wirings onthe substrate in the solder resist coating of the circuit board.

Examples of the colorant (e) used in the present invention include adye, a thermo-sensitive dye, an inorganic pigment, and an organicpigment. Preferable colorants are soluble in an organic solvent thatdissolves the component (a) and are compatible with resins. Of thesecolorants, dyes are, for example, an oil-soluble dye, a disperse dye, areactive dye, an acid dye, and a direct dye. The skeleton of the dye maybe formed of an anthraquinone dye, an azo dye, a phthalocyanine dye, amethine dye, or an oxazine dye. These dyes may each contain a metalcomplex salt. Preferably, a phthalocyanine dye or ametal-complex-salt-containing dye is used from the viewpoint ofexcellent heat resistant and light resistant properties. Specificexamples of such dyes include Sumilan and Lanyl dyes (Sumitomo ChemicalIndustry Co., Ltd.), Orasol, Oracet, Filamid, and Irgasperse dyes (CibaSpecialty Chemicals Co., Ltd.), Zapon, Neozapon, Neptune, and Acidoldyes (BASF), Kayaset and Kayakalan dyes (Nippon Kayaku Co., Ltd.),Valifast colors dyes (Orient Chemical Co., Ltd.), Savinyl, Sandoplast,Polysynthren, and Lanasyn dyes (Clariant Japan Co., Ltd.), and AizenSpilon dyes (Hodogaya Chemical Co., Ltd.). These dyes may be used aloneor in combination.

The thermo-sensitive dye that is used in the present inventionpreferably develops color via heating and exhibits the absorption peakat 350 nm to 700 nm, which may be a general thermo-sensitive dye orpressure-sensitive dye. Examples of such thermo-sensitive dye includethose which develop color by changing the chemical structures or stateof electric charge by the action of acidic groups exiting in the systemduring heating, and those which develop color by thermal oxidationreaction or the like with the oxygen in the air. Examples of theskeleton structure of the thermo-sensitive dye include a triarylmethaneskeleton, a diarylmethane skeleton, a fluorane skeleton, a bislactoneskeleton, a phthalide skeleton, a xanthene skeleton, a rhodamine lactamskeleton, a fluorene skeleton, a phenothiazine skeleton, a phenoxazineskeleton, and a spiropyran skeleton.

Specific examples of the thermo-sensitive dyes of the present inventioninclude 4,4′,4″-tris(dimethylamino)triphenylmethane,4,4′,4″-tris(diethylamino)-2-,2′,2″-trimethyltriphenylmethane,2,4′,4″-methylidenetrisphenol, 4,4′,4″-methylidenetrisphenol,4,4′-[(4-hydroxyphenyl)methylene]bis(benzeneamine),4,4′-[(4-aminophenyl)methylene]bisphenol,4,4′-[(4-aminophenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4,4′-[(3-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxyphenyl)methylene]bis[2,3,5-trimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)methyl]-1,2-benzenediol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakisphenol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2-methylphenol],4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2,6-dimethylphenol],4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakisphenol,4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol),4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],2,2′-[(3-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5-dimethylphenol],2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylethylphenol],4,4′-[(3-hydroxyphenyl)methylene]bis[2-methylethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylethylphenol],2,2′-[(3-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],4,4′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(methyl ethyl)phenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-5-methylphenol],4,4′ [(2-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(3-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-6-methylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′,4″-methylidenetris[2-cyclohexyl-5-methylphenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-cyclohexylphenol],3,3′-[(2-hydroxyphenyl)methylene]bis[5-methylbenzene-1,2-diol],4,4′-[4-[[bis(4-hydroxy-2,5-dimethylphenyl)methyl]phenyl]methylene]bis[1,3-benzenediol],4,4′-methylenebis[2-[di(4-hydroxy-3-methylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-2,5-dimethylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-3,5-dimethylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(3-cyclohexyl-4-hydroxy-6-methylphenyl)]methyl]phenol,4,4′-(3,5-dimethyl-4-hydroxyphenylmethylene)-bis(2,6-dimethylphenol),3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,3,6-bis(dimethylamino)fluorane-γ-(4′-nitro)-aminolactam,2-(2-chloroanilino)-6-diethylaminofluorane,2-(2-chloroanilino)-6-dibutylaminofluorane,2-N,N-dibenzylamino-6-diethylaminofluorane, 6-diethylamino-benzo[a]-fluorane,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-bi(imidazole),1,3-dimethyl-6-diethylaminofluorane,2-anilino-3-methyl-6-dibutylaminofluorane,3,7-bis(dimethylamino)-10-benzoylphenothiazine,3-diethylamino-6-chloro-7-(β-ethoxyethylamino)fluorane,3-diethylamino-6-methyl-7-anilinofluorane,3-triethylamino-6-methyl-7-anilinofluorane, and3-cyclohexylamino-6-methyl-7-anilinofluorane.

Among these compounds, hydroxyl-group-containing compounds having atriarylmethane skeleton, such as 2,4′,4″-methylidenetrisphenol,4,4′,4″-methylidenetrisphenol,4,4′-[(4-hydroxyphenyl)methylene]bis(benzeneamine),4,4′-[(4-aminophenyl)methylene]bisphenol,4,4′-[(4-aminophenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4,4′-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxyphenyl)methylene]bis[2,3,5-trimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)methyl]-1,2-benzenediol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakisphenol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2-methylphenol],4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2,6-dimethylphenol],4,4′,4′,4′″-(1,4-phenylenedimethyl idene)tetrakisphenol,4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol),4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-5-methylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-6-methylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′,4″-methylidenetris[2-cyclohexyl-5-methylphenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-cyclohexylphenol],3,3′-[(2-hydroxyphenyl)methylene]bis[5-methylbenzene-1,2-diol],4,4′-[4-[[bis(4-hydroxy-2,5-dimethylphenyl)methyl]phenyl]methylene]bis[1,3-benzenediol],4,4′-methylenebis[2-[di(4-hydroxy-3-methylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-2,5-dimethylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-3,5-dimethylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(3-cyclohexyl-4-hydroxy-6-methylphenyl)]methyl]phenol,and4,4′-(3,5-dimethyl-4-hydroxyphenylmethylene)-bis(2,6-dimethylphenol),are particularly preferable in terms of their excellent heat resistance.They may be used alone or in combination.

Color development of thermo-sensitive dye compounds is preferablyinduced by heat at a temperature higher than 120° C., and morepreferably higher than 180° C. A thermo-sensitive compound having ahigher color-developing temperature has better heat resistance at hightemperature, and has better light fastness since discoloration is lesslikely to occur due to irradiation with ultraviolet or visible radiationfor a long period of time.

The organic pigment used in the present invention preferably exhibitsgood coloration and high heat resistance. In particular, it ispreferable that the organic pigment comprises carbon black and/or acombination of two or more organic pigments. Examples of such carbonblacks include: furnace blacks, such as HCF, MCF, LFF, RCF, SAF, ISAF,HAF, XCF, FEF, GPF, and SRF; thermal blacks, such as FT and MT; channelblacks; and acetylene blacks. These carbon blacks may be used alone orin combinations of two or more.

Preferably, the organic pigments that are used in the present inventionhave excellent heat resistance. Specific examples of representativepigments are listed below by color index (CI) numbers. Yellow pigmentsinclude, for example, Pigment Yellows 12, 13, 14, 17, 20, 24, 31, 55,83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153,154, 155, 166, 168, 173, 180, and 185. Orange pigments include, forexample, Pigment Oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64,65, and 71. Red pigments include, for example, Pigment Reds 9, 97, 122,123, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224,242, and 254. Violet pigments include, for example, Pigment Violets 19,23, 29, 32, 33, 36, 37, and 38. Blue pigments include, for example,Pigment Blues 15 (15:3, 15:4, 15:6), 21, 22, 60, and 64. Green pigmentsinclude, for example, Pigment Greens 7, 10, 36, and 47.

The inorganic pigment that is used in the present invention ispreferably an insulative metal compound. Use of an inorganic pigmentwith poor electric insulating capacity results in insufficient functionsas an insulation film of an organic electroluminescent device. If aluminescent element is prepared, such a pigment could cause a shortcircuit that results in a serious problem. Such insulative metalcompounds include manganese oxide, titanium oxide, titanium oxidenitride, chromium oxide, vanadium oxide, iron oxide, cobalt oxide, andniobium oxide. Among these compounds, manganese oxide and titanium oxidenitride are preferable in the present invention. The manganese oxide isgenerally expressed by Mn_(x)O_(y) (1<y<x≦2). Specifically, themanganese oxide may be γ-MnO₂, β-MnO₂, α-MnO₂, Mn₂O₃, or Mn₃O₄.Amorphous Mn_(x)O_(y) (1<y<x≦2) may also be used. Preferably, theprimary particle size of the manganese oxide is 100 nm or less, and morepreferably 60 nm or less. The primary particle size can be determined bythe arithmetic mean using an electron microscope.

Titanium oxide nitride that is preferably used in the present inventiongenerally has a composition expressed by TiN_(α)O_(β) (0<α<2, 0.1<β<2).The primary particle size of the titanium oxide nitride is preferably100 nm or less, and more preferably 60 nm or less, as with the manganeseoxide.

The amount of the colorant (e) of the present invention to be added ispreferably 0.2 to 100 parts by weight, and more preferably 0.4 to 70parts by weight, based on 100 parts by weight of the component (a). Whenthe amount the colorant (e) to be added is larger than 100 parts byweight based on 100 parts by weight of the component (a), the resincontent becomes too small, which deteriorates the adhesion of thephotosensitive resin film to the substrate. When such amount is smallerthan 0.2 parts by weight, the photosensitive resin film loses itsfunction as a shield.

In the present invention, the surfaces of the organic pigments and theinorganic pigments may be treated with rosin, an acidic group, a basicgroup, or the like, according to need. The pigment can be used togetherwith a dispersant. Examples of a dispersant include cationic, anionic,nonionic, amphoteric, silicone, and fluorine surfactants.

The colorant as the component (e) of the photosensitive resincomposition according to the present invention functions as a solderresist coating, light-shading separator of an organic electroluminescentdisplay unit or a liquid crystal display unit, black matrix, or shield.In order to exhibit such functions, the colorant preferably exhibitsabsorption in a wide region covering from the infrared region to theultraviolet region according to the applications. Coloring can becarried out with the use of at least one type of dye or pigment, acombination of two or more types of dyes or two or more types ofpigments, or a combination of at least one type of dye or pigment withat least one other type of dye or pigment.

Further, a compound having a phenolic hydroxyl group can be incorporatedin order to control the alkali developability of the composition.

Examples of compounds having a phenolic hydroxyl group that can be usedin the present invention include Bis-Z, Bis OC-Z, Bis OPP-Z, Bis P-CP,Bis26X-Z, Bis OTBP-Z, Bis OCHP-Z, Bis OCR-CP, Bis P-MZ, Bis P-EZ,Bis26X-CP, Bis P-PZ, Bis P-IPZ, Bis CR-IPZ, Bis OCP-IPZ, Bis OIPP-CP,Bis26X-IPZ, Bis OTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), Tris P-HAP,Tris P-PA, Bis OFP-Z, Bis RS-2P, Bis PG-26×, Bis RS-3P, Bis OC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, Bis OCHP-OC, Bis236T-OCHP,methylenetris-FR-CR, Bis RS-26×, and Bis RS-OCHP (trade names, HonshuChemical Industry Co., Ltd.), and BIR-OC, BIP-PC, BIR-PC, BIR-PTBP,BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (trade names, AsahiOrganic Chemicals Industry Co., Ltd.).

Among these compounds, preferable phenolic hydroxyl-group-containingcompounds are, for example, Bis-Z, Bis P-EZ, TekP-4HBPA, Tris P-HAP,Tris P-PA, Bis OCHP-Z, Bis P-MZ, Bis P-PZ, Bis P-IPZ, Bis OCP-IPZ, BisP-CP, Bis RS-2P, Bis RS-3P, Bis P-OCHP, methylenetris-FR-CR, Bis RS-26×,BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F. Bis-Z, TekP-4HBPA, Tris P-HAP,Tris P-PA, Bis RS-2P, Bis RS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F, and thelike are particularly preferable. With the addition of such compound,the resulting resin composition is easily soluble in an alkalinedeveloper before exposure and becomes hardly soluble therein byexposure. Consequently, a reduction in film thickness caused bydeveloping is small and developing can be readily completed within ashort period of time.

The content of the compound having a phenolic hydroxyl group ispreferably in the range of 1 to 60 parts by weight, and more preferablyin the range of 3 to 50 parts by weight, based on 100 parts by weight ofthe polymer.

In addition, in order to enhance the wettability between thephotosensitive resin composition and a substrate, a surfactant, esters,such as ethyl lactate or propylene glycol monomethyl ether acetate,alcohols, such as ethanol, ketones, such as cyclohexanone or methylisobutyl ketone, or ethers, such as tetrahydrofuran or dioxane may beadded, according to need. Also, inorganic particles of silicon dioxide,titanium dioxide, or the like or polyimide powder may be added.

Furthermore, in order to enhance adhesion with a base substrate such asa silicon wafer, 0.5 to 10% by weight of a silane coupling agent or atitanium chelating agent may be added to a varnish, which is thephotosensitive resin composition. Alternatively, the base substrate maybe subjected to pretreatment with such chemical.

When adding a chemical to the varnish, a silane coupling agent, such asmethylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, atitanium chelating agent, or an aluminum chelating agent is added in anamount of 0.5 to 10% by weight based on the amount of the polymer in thevanish.

When treating the substrate, the aforementioned coupling agent isdissolved in a solvent such as isopropanol, ethanol, methanol, water,tetrahydrofuran, propylene glycol monomethyl ether acetate, propyleneglycol monomethyl ether, ethyl lactate, or diethyl adipate in amounts of0.5 to 20% by weight thereof. The resulting solution is applied to thesurface of the substrate via spin coating, immersion, spray coating, orsteaming. In some cases, the coupling agent and the substrate are heatedto a temperature of 50° C. to 300° C. to allow the reaction of thecoupling agent with the substrate to proceed.

The photosensitive resin composition of the present invention does notcomprise an onium salt, diallyl compound, or tetraalkylammonium salt inorder to block the dissolution of the component (a) in an aqueousalkaline solution. When such substance is contained, decomposition takesplace at the time of subsequent heat treatment, and an acid or base isgenerated. This can deteriorate the properties of the resulting film,such as heat resistance, mechanical properties, and adhesiveness.

In the present invention, the components (a) to (e) and a compoundhaving phenolic hydroxyl group are used while being dissolved and/ordispersed in an organic solvent.

An organic solvent used herein preferably has a boiling point of 80° C.to 250° C. at atmospheric pressure.

Examples of the organic solvent used in the present invention include:ethers, such as ethylene glycol monomethyl ether, ethyleneglycolmonoethyl ether, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycoldiethyl ether, and ethylene glycol dibutylether; acetates, such asethylene glycol monoethyl ether acetate, propylene glycol monomethylether acetate, propyl acetate, butyl acetate, isobutyl acetate,3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate,ethyl lactate, and butyl lactate; ketones, such as acetylacetone,methylpropylketone, methylbutylketone, methylisobutylketone,cyclopentanone, and 2-heptanone; alcohols, such as butyl alcohol,isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol,3-methyl-3-methoxy butanol, and diacetone alcohol; aromatichydrocarbons, such as toluene and xylene; and N-methyl-2-pyrrolidone,N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide,N,N-dimethylacetamide, dimethylsulfoxide, and γ-butyrolactone. Amongthem, compounds capable of dissolving the component (a) and having aboiling point of 100° C. to 180° C. at atmospheric pressure areparticularly preferable. If a boiling point is lower than 100° C., sometype of composition may not be applied because of vaporization of asolvent at the time of coating. If a boiling point exceeds 180° C., thetemperature at which the composition is heat-treated becomes high, andthe material of the base substrate is disadvantageously restricted inpractical use. Also, use of a solvent capable of dissolving component(a) enables the formation of a homogenous coating as a base substrate.

Specific examples of particularly preferable solvents includecyclopentanone, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, propylene glycol monomethyl ether, methyl lactate,ethyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol.

The amount of the organic solvent used in the resin composition of thepresent invention is preferably 20 to 800 parts by weight, and morepreferably 30 to 500 parts by weight, based on 100 parts by weight ofthe polymer in the component (a). They may be used alone or incombination.

Subsequently, a method for forming heat resistant resin patterns usingthe photosensitive composition of the present invention is described.

The photosensitive resin composition is applied to a substrate. Asilicon wafer, ceramics, gallium arsenide, and the like are used as thesubstrate, although the substrate is not limited thereto. Thecomposition may be applied via, for example, spin coating with spinner,spray coating, or roll coating. The thickness of the coated film dependson a means of application, a solid content in the composition, theviscosity of the composition, and the like. Coating is generally appliedto a thickness of 1 to 150 μm on a dry basis.

The substrate coated with the photosensitive resin composition is thendried to form a film of the photosensitive resin composition. Drying ispreferably performed at a temperature of 50° C. to 150° C. for a periodof 1 minute to several hours using an oven, a hot plate, infrared rays,or the like.

The film of the photosensitive resin composition is then exposed toactinic rays through a mask having a desired pattern. Ultraviolet light,visible light, electron rays, and X rays are generally used as theactinic rays. In the present invention, i rays (365 nm), h rays (405nm), or g rays (436 nm) from a mercury vapor lamp is preferably used.

In order to form a pattern of resin composition, unexposed regions ofthe film are removed with a developer after developing.

As the developer, for example, N-methyl-2-pyrrolidone,N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, or hexamethylphosphortriamide may be used alone.Alternatively, such developer may be dissolved in: for example, organicsolvents, such as methanol, ethanol, isopropyl alcohol, methyl carbitol,ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate,propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate,ethyl-3-ethoxypropionate, 2-heptanone, or ethyl acetate; an aqueoussolution of tetramethylammonium; or an aqueous solution of an alkalinecompound, such as diethanolamine, diethylaminoethanol, sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate,triethylamine, diethylamine, methylamine, dimethylamine,dimethylaminoethyl acetate, dimethylaminoethanol,dimethylaminoethylmethacrylate, cyclohexylamine, ethylenediamine, orhexamethylenediamine. Particularly preferably, the developer isdissolved in an aqueous solution of tetramethylammonium and an aqueoussolution of an alkaline compound such as diethanolamine,diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, or triethylamine. If necessary, theaforementioned aqueous alkaline solution may be combined with a singletype or a combinations of two or more of polar solvents, such asN-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, γ-butyrolactone, or dimethylacrylamide, alcohols,such as methanol, ethanol, or isopropanol, esters, such as ethyllactate, or propylene glycol monomethyl ether acetate, or ketones, suchas cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutylketone. After developing, the substrate is rinsed with water. Water maycontain alcohols, such as ethanol or isopropyl alcohol, or esters, suchas ethyl lactate or propylene glycol monomethyl ether acetate.

If the resolution of a developed pattern is improved or the permissiblerange of developing conditions is widened, a step of baking may beadditionally carried out before developing. This process is preferablycarried out at 50° C. to 180° C., and more preferably at 60° C. to 150°C. The duration thereof is preferably between 10 seconds and severalhours. Beyond such ranges, the reaction may not be proceeded, or all theregions may not be dissolved. Accordingly, it must be proceeded withcaution.

After developing, a resin film is formed by heating at 120° C. to 280°C. Heat treatment is carried out by gradually raising the temperature byselecting the temperatures or continuously raising the temperature byselecting a given range of temperature for 5 minutes to 5 hours. Forexample, heat treatment is carried out by heating at 130° C., 200° C.,and 350° C. for 30 minutes each. Alternatively, temperature is linearlyraised from room temperature to 400° C. over the period of 2 hours.

The heat resistant resin film prepared from the photosensitive resincomposition of the present invention is used as a passivation film ofsemiconductors, a protective film of semiconductor devices, aninterlayer insulation film of multilayer wirings for high-densitypacking, an insulation layer for protecting wirings of the circuitboard, and other films.

The composition of the present invention can be used as an insulationlayer provided for a display unit. For example, a display unitcomprising an insulation layer comprises a first electrode formed on asubstrate and a second electrode provided opposing the first electrode.Specific examples of display units include those comprising LCD, ECD,ELD, and an organic electroluminescent element (an organicelectroluminescent device).

EXAMPLES

It should be noted that the present invention is not limited to theseexamples. The photosensitive resin composition and the like wereevaluated in the following manner.

Measurement of the Rate of Imide Conversion

The rate of imide conversion of the polymer used was calculated in thefollowing manner. At the outset, the infrared absorption spectrum of thepolymer was measured, and the absorption peaks of the polyimide imidestructure were detected at around 1780 cm¹ and 1377 cm⁻¹. Subsequently,the polymer was subjected to heat treatment at 350° C. in a nitrogenatmosphere for 1 hour, the infrared absorption spectrum was measuredafter heat treatment, and the obtained peak intensity at around 1377cm⁻¹ was compared with the intensity before heat treatment to determinethe rate of imide conversion in the polymer before heat treatment.

Formation of Photosensitive Resin Film

The photosensitive resin composition (hereinafter referred to as avarnish) was applied onto a 6-inch silicon wafer so that the thicknessof the film would be 30 μm after prebaking, and was then prebaked at100° C. for 2 minutes on a hot plate (Mark-7, Tokyo Electron Limited) toform a photosensitive resin film.

Measurement of Film Thickness

The thickness was measured at a refractive index of 1.73 using RamdaASTM-602 (Dainippon Screen Mfg. Co., Ltd.).

Exposure

A reticle having an incised pattern was set in an exposing machine(Spectrum 3e, all-wavelength stepper, Ultratech), and exposure wascarried out in all wavelength ranges at an intensity of 700 mJ/cm² (interms of i-line).

Post-Exposure Baking

Before developing, the exposed film was subjected to post-exposurebaking on a hot plate (Mark-7, Tokyo Electron Limited) at 60° C. for 1minute.

Developing

An aqueous solution of 2.38% tetramethylammonium hydroxide was sprayedfor 10 seconds at 50 rotations using a developing machine of Mark-7(Tokyo Electron Ltd.). The film was then allowed to stand for 60 secondsat 0 rotation, rinsed with water at 400 rotations, and dried by spinningfor 10 seconds at 3,000 rotations.

Heat Treatment (Curing)

The developed film was subjected to heat treatment using an inert ovenINH-21CD (Koyo Thermo Systems Co., Ltd.) at temperature and the timedescribed in examples.

Calculation of the Film Retentivity

The film retentivity was calculated according to the following equation:Film retentivity (%)=thickness of developed film/thickness pre-bakedfilm×100

Calculation of the Film Retentivity After Shrinkage

The film retentivity after shrinkage was calculated according to thefollowing equation.Film retentivity after shrinkage (%)=thickness of heat-treatedfilm/thickness of developed film×100

Crack Resistance

The developed film was subjected to heat treatment under arbitraryconditions, and whether or not the corner of the 50-μm □ punched pattern(i.e., a punched pattern of 50 μm×50 μm) was cracked (n=5) was observedunder an optical microscope.

Stress Resistance

The developed film was subjected to heat treatment under arbitraryconditions, and whether or not the corner of the 50-μm □ left pattern(i.e., a left pattern of 50 μm×50 μm) was wrinkled (n=5) was observedunder an optical microscope.

Synthetic Example 1 Synthesis of Activated Ester Compound (I)

In a dry nitrogen gas stream, 18.5 g (0.1 mol) of 4-carboxybenzoic acidchloride and 13.5 g (0.1 mol) of hydroxybenzotriazole were dissolved in100 g of tetrahydrofuran (THF), and the solution was cooled to −15° C. Asolution of 10 g (0.1 mol) of triethylamine in 50 g of THF was addeddropwise thereto, so that the temperature of the reaction solution didnot exceed 0° C. After the dropwise addition, the mixture was allowed toreact at 25° C. for 4 hours. The reaction solution was concentrated witha rotary evaporator to obtain an activated ester compound (I).

Synthetic Example 2 Synthesis of Hydroxyl-Group-Containing AcidAnhydride (II)

In a dry nitrogen gas stream, 18.3 g (0.05 mol) of2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF) and 34.2 g (0.3mol) of allyl glycidyl ether were dissolved in 100 g of gammabutyrolactone (GBL), and the resulting solution was cooled to −15° C.Subsequently, a solution of 22.1 g (0.11 mol) of trimellitic anhydridechloride in 50 g of GBL was added dropwise thereto, so that thetemperature of the reaction solution did not exceed 0° C. After thedropwise addition, the mixture was allowed to react at 0° C. for 4hours. The reaction solution was concentrated with a rotary evaporator,and the concentrated solution was added to 1 l of toluene to obtain theacid anhydride (II).

Synthetic Example 3 Synthesis of Hydroxyl-Group-Containing DiamineCompound (III)

BAHF (18.3 g, 0.05 mol) was dissolved in 100 ml of acetone and 17.4 g(0.3 mol) of propylene oxide, and the resulting solution was cooled to−15° C. Subsequently, a solution of 20.4 g (0.11 mol) of 4-nitrobenzoylchloride in 100 ml of acetone was added dropwise thereto. After thedropwise addition, the mixture was allowed to react at −15° C. for 4hours and the temperature of the mixture was then allowed to return toroom temperature. White solid deposits were separated by filtration andwere dried in vacuo at 50° C.

The solid (30 g) was placed in a 300 ml stainless-steel autoclave,dispersed in 250 ml of methyl cellosolve, and then blended with 2 g of5% palladium-carbon. Hydrogen was introduced thereto by a balloon, and areduction reaction was performed at room temperature. Approximately 2hours thereafter, it was ensured that the balloon did not deflate anymore, and the reaction was terminated. After the termination of thereaction, a palladium compound as a catalyst was removed by filtration,and the reaction solution was concentrated with a rotary evaporator toobtain a diamine compound (III). The obtained solid was used in thereaction in such a state.

The compounds having phenolic hydroxyl groups used in the Examples andcomparative examples are shown below.

Example 1

In a dry nitrogen gas stream, 11.41 g (0.057 mol) of4,4′-diaminodiphenyl ether, 1.24 g (0.005 mol) of1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 8.18 g (0.075 mol) of3-aminophenol (Tokyo Kasei Kogyo Co., Ltd.) as an endcap agent weredissolved in 80 g of N-methyl-2-pyrrolidone (NMP).Bis(3,4-dicarboxyphenyl)ether dianhydride (31.02 g, 0.1 mol) and 20 g ofNMP were added thereto, and the mixture was allowed to react at 20° C.for 1 hour and then at 50° C. for 4 hours. Thereafter, 15 g of xylenewas added thereto, water was subjected to azeotropy with xylene, and themixture was agitated at 150° C. for 5 hours. After the completion ofagitation, the solution was poured into 3 l of water, and white depositswere collected by filtration. The collected deposits were washed threetimes with water and dried in a vacuum dryer at 80° C. for 20 hours. Theresulting polymer solid was subjected to infrared absorption spectrummeasurement, and the absorption peaks of the polyimide imide structurewere detected at around 1780 cm⁻¹ and 1377 cm⁻¹. The rate of imideconversion of the polymer solid mixture thus obtained was inspected.

Subsequently, 10 g of this polymer solid, 0.5 g of a photopolymerizationinitiator, i.e., bis(α-isonitrosopropiophenone oxime)isophthal, 1 g of athermally crosslinkable compound Nikalac MX-270 (trade name, SanwaChemical Co., Ltd.), 2 g of Tris P-PA, and 5 g of trimethylolpropanediacrylate (a compound having a polymerizable functional groupcomprising unsaturated double bonds) were dissolved in 12 g of ethyllactate to prepare a varnish A, which is a negative-workingphotosensitive polyimide composition. With the use of this varnish, aphotosensitive polyimide film was formed on a silicon wafer as describedabove, exposed, post-exposure baked, developed in an alkaline developer,and then heat treated at 170° C. for 60 minutes. The alkalinedevelopability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 2

In a dry nitrogen gas stream, 49.57 g (0.082 mol) of thehydroxyl-group-containing diamine compound (III), which was obtained inSynthetic Example 3, and 9.9.1 g (0.035 mol) of the activated estercompound (I) as an endcap agent were dissolved in 150 g of NMP.Bis(3,4-dicarboxyphenyl)ether dianhydride (31.02 g, 0.1 mol) and 30 g ofNMP were added thereto, and the mixture was allowed to react at 20° C.for 1 hour and then at 50° C. for 4 hours. Thereafter, the mixture wasagitated at 180° C. for 5 hours. After the completion of agitation, thesolution was poured into 3 l of water, and white deposits were collectedby filtration. The collected deposits were washed three times with waterand dried in a vacuum dryer at 80° C. for 20 hours. The resultingpolymer solid was subjected to infrared absorption spectrum measurement,and the absorption peaks of the polyimide imide structure were detectedat around 1780 cm⁻¹ and 1377 cm⁻¹. The rate of imide conversion of thepolymer solid mixture thus obtained was inspected.

Subsequently, 10 g of the polymer solid, 2 g of a photopolymerizationinitiator, i.e.,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 5 g ofpentaerythritol triacrylate (a compound having a polymerizablefunctional group comprising unsaturated double bonds), and 1 g ofvinyltrimethoxysilane were dissolved in 10 g of γ-butyrolactone toprepare a varnish B, which is a negative-working photosensitivepolyimide composition. With the use of this varnish, a photosensitivepolyimide film was formed on a silicon wafer as described above,exposed, post-exposure baked, developed in an alkaline developer, andthen heat treated at 200° C. for 60 minutes. The alkaline developabilityof the varnish, the film retentivity, the film retentivity aftershrinkage, the crack resistance, and stress resistance were evaluated.

Example 3

In a dry nitrogen gas stream, 46.55 g (0.077 mol) of thehydroxyl-group-containing diamine compound (III), which was obtained inSynthetic Example 3, was dissolved in 250 g of NMP. Thehydroxyl-group-containing acid anhydride (II) (71.45 g, 0.1 mol), whichwas obtained in Synthetic Example 2, and 7.38 g (0.045 mol) of3-hydroxyphthalic anhydride (Tokyo Kasei Kogyo Co., Ltd.) as an endcapagent were added thereto, and the mixture was allowed to react at 60° C.for 6 hours. Thereafter, 15 g of xylene was added thereto, the reactionsolution was subjected to azeotropy with xylene, and the mixture wasagitated at 150° C. for 5 hours. After the completion of agitation, thesolution was poured into 2 l of water, and white deposits were collectedby filtration. The collected deposits were washed three times with waterand dried in a vacuum dryer at 80° C. for 20 hours. The resultingpolymer solid was subjected to infrared absorption spectrum measurement,and the absorption peaks of the polyimide imide structure were detectedat around 1780 cm⁻¹ and 1377 cm⁻¹. The rate of imide conversion of thepolymer solid mixture thus obtained was inspected.

Subsequently, 10 g of the polymer solid, 2.5 g of a photopolymerizationinitiator, i.e.,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 8 g ofpentaerythritol triacrylate (a compound having a polymerizablefunctional group comprising unsaturated double bonds), 5 g of athermally crosslinkable compound DML-PC (trade name, Honshu ChemicalIndustry Co., Ltd.), and 1 g of vinyltrimethoxysilane were dissolved in10 g of 3-methyl-3-methoxy butanol to prepare a varnish C, which is anegative-working photosensitive polyimide composition. With the use ofthis varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 180° C. for 60 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 4

In a dry nitrogen gas stream, 40.5 g (0.067 mol) of thehydroxyl-group-containing diamine compound (III), which was obtained inSynthetic Example 3, and 1.24 g (0.005 mol) of1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 130 g ofNMP. 3,3′, 4,4′-Biphenyltetracarboxylic acid dianhydride (29.42 g, 0.1mol) and 20 g of NMP were added thereto, and the mixture was allowed toreact at 20° C. for 1 hour and then at 50° C. for 2 hours.4-Aminothiophenol (6.89 g, 0.055 mol, Tokyo Kasei Kogyo Co., Ltd.) wasadded thereto, and the mixture was agitated at 50° C. for 2 hours andthen at 180° C. for 5 hours. After the completion of agitation, thesolution was poured into 3 l of water, and white deposits were collectedby filtration. The collected deposits were washed three times with waterand dried in a vacuum dryer at 80° C. for 20 hours. The resultingpolymer solid was subjected to infrared absorption spectrum measurement,and the absorption peaks of the polyimide imide structure were detectedat around 1780 cm⁻¹) and 1377 cm⁻¹. The rate of imide conversion of thepolymer solid mixture thus obtained was inspected.

Subsequently, 10 g of the polymer solid, 0.2 g of a photopolymerizationinitiator, i.e., N-phenylglycine, 0.4 g of bis(α-isonitrosopropiophenoneoxime)isophthal, 0.3 g of a thermally crosslinkable compound TML-HQ(trade name, Honshu Chemical Industry Co., Ltd.), and 5.5 g ofdimethylol-tricyclodecane diacrylate, (a compound having a polymerizablefunctional group comprising unsaturated double bonds), were dissolved in13 g of propylene glycol monomethyl ether to prepare a varnish D, whichis a negative-working photosensitive polyimide composition. With the useof this varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 150° C. for 60 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 5

In a dry nitrogen gas stream, 30.03 g (0.082 mol) of2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 1.24 g (0.005mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2.73 g (0.025mol) of 3-aminophenol (Tokyo Kasei Kogyo Co., Ltd.) as an endcap agentwere dissolved in 100 g of NMP. Bis(3,4-dicarboxyphenyl)etherdianhydride (31.02 g, 0.10 mol) and 30 g of NMP were added thereto, andthe mixture was allowed to react at 20° C. for 1 hour and then at 50° C.for 4 hours. The reaction product was then agitated at 180° C. for 5hours. After the completion of agitation, the solution was poured into 3l of water, and white deposits were collected by filtration. Thecollected deposits were washed three times with water and dried in avacuum dryer at 200° C. for 5 hours. The resulting polymer solid wassubjected to infrared absorption spectrum measurement, and theabsorption peaks of the polyimide imide structure were detected ataround 1780 cm⁻¹ and 1377 cm⁻¹. The rate of imide conversion of thepolymer solid mixture thus obtained was inspected.

Subsequently, 10 g of the polymer solid, 0.4 g of a photopolymerizationinitiator, i.e., 1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), 1.5 g of a thermally crosslinkable compound Nikalac MW-100 LM(trade name, Sanwa Chemical Co., Ltd.), 0.3 g of an A-DMA colorant(trade name, Hodogaya Chemical Co., Ltd.), and 10 g oftrimethylolpropane triacrylate (a compound having a polymerizablefunctional group comprising unsaturated double bonds) were dissolved in10 g of diacetone alcohol to prepare a varnish E, which is anegative-working photosensitive polyimide composition. With the use ofthis varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 180° C. for 60 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 6

The polymer solid obtained in Example 3 (10 g), 3 g of aphotopolymerization initiator, i.e.,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 0.1 g of anOil Blue 2N colorant (trade name, Orient Chemical Co., Ltd.), 0.2 g of aCVL colorant (trade name, Hodogaya Chemical Co., Ltd.), 3.5 g ofdimethylol-tricyclodecane diacrylate (a compound having a polymerizablefunctional group comprising unsaturated double bonds), and 1.5 g oftrimethylolpropane diacrylate were dissolved in 13 g of ethyl lactate toprepare a varnish F, which is a negative-working photosensitivepolyimide composition. With the use of this varnish, a photosensitivepolyimide film was formed on a silicon wafer as described above,exposed, post-exposure baked, developed in an alkaline developer, andthen heat treated at 200° C. for 60 minutes. The alkaline developabilityof the varnish, the film retentivity, the film retentivity aftershrinkage, the crack resistance, and stress resistance were evaluated.

Example 7

The polymer solid obtained in Example 4 (10 g), 1 g of aphotopolymerization initiator, i.e.,1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1.7 g of athermally crosslinkable compound DMOM-PTBP (trade name, Honshu ChemicalIndustry Co., Ltd.), 1.5 g of BIR-PC (trade name, Asahi OrganicChemicals Industry Co., Ltd.), 0.7 g ofN-(3-diethylaminopropyl)methacrylamide (a compound having apolymerizable functional group comprising unsaturated double bonds), and4.5 g of dimethylol-tricyclodecane diacrylate were dissolved in 12 g ofγ-butyrolactone and 8 g of cyclopentanone to prepare a varnish G, whichis a negative-working photosensitive polyimide composition. With the useof this varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 210° C. for 30 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 8

The polymer solid obtained in Example 5 (10 g), 0.5 g of aphotopolymerization initiator, i.e.,1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 0.8 g of athermally crosslinkable compound B-a type benzoxazine (trade name,Shikoku Chemicals Corp.), 2.5 g of BIR-PC (trade name, Asahi OrganicChemicals Industry Co., Ltd.), and 4 g of N-vinylcaprolactam and 2.5 ofdimethylol-tricyclodecane diacrylate, which are each a compound having apolymerizable functional group comprising unsaturated double bonds, weredissolved in 15 g of diacetone alcohol to prepare a varnish H, which isa negative-working photosensitive polyimide composition. With the use ofthis varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 180° C. for 30 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 9

An indium tin oxide (ITO) transparent electrode film having a thicknessof 130 nm was formed on the surface of no-alkali glass having athickness of 1.1 mm by means of sputtering vapor deposition so as toprepare a glass substrate. The glass substrate was cut into 120×100 mm.A photoresist was applied on the ITO substrate, and patterning wascarried out via exposure and developing by a common photolithographicmethod. The unnecessary portions of the ITO were removed by etching, andthe photoresist was then removed to form a striped pattern on the ITOfilm. The resulting striped first electrode had a pitch of 100 μm.

The density of the varnish A prepared in Example 1 was then adjustedwith ethyl lactate. The adjusted varnish A was applied on the firstelectrodes on the substrate by means of spin-coating and was pre-bakedon a hot plate at 100° C. for 3 minutes. The resulting film was exposedto UV light through a photomask, and the exposed portion was exclusivelydissolved and developed in an aqueous solution of 2.38% TMAH. Theresulting film was rinsed with pure water to obtain a polyimide pattern.The polyimide pattern was cured by heating in a nitrogen atmosphere in aclean oven at 170° C. for 30 minutes, and then at 170° C. for 60 minutesso as to form an insulation layer that covers the edges of the firstelectrodes. The thickness of the insulation layer was approximately 1μm.

An organic electroluminescent device was prepared using the substrateprovided with the insulation layer. A thin-film layer comprising aluminescent layer was vacuum-deposited by a resistance-wire heatingmethod. A hole transport layer was formed on the entire effective areaof the substrate by vapor deposition. A luminescent layer and analuminum second electrode were formed with the use of a shadow mask.

The aforementioned substrate was removed from the deposition device. Thesubstrate was bonded to a sealing glass plate with the aid of a curableepoxy resin so as to seal the substrate. Thus, a simple-matrix colororganic electroluminescent device having a striped first electrodecomposed of ITO, a patterned luminescent layer formed on the firstelectrode, and a striped second electrode orthogonal to the firstelectrode was prepared. When this display unit was drivenline-sequentially, good display characteristics were obtained. At theborder areas of the insulation layer, neither the thin-film layer northe second electrode suffered from thinning or stepped cuts, and theywere deposited without trouble. As a result, the brightness within theluminescent region was even, and stable light emission was achieved.Moreover, the cross-section had a forward tapered shape.

Example 10

A simple-matrix color organic electroluminescent device was prepared inthe same manner as in Example 9, except that the varnish C prepared inExample 3 was used and the curing was performed at 180° C. for 30minutes. When the resulting device was driven line-sequentially, nodegradation in the brightness was observed, and good displaycharacteristics were obtained.

Example 11

A simple-matrix color organic electroluminescent device was prepared inthe same manner as in Example 9, except that the varnish E prepared inExample 5 was used and the curing was performed at 200° C. for 30minutes. When the resulting device was driven line-sequentially, nodegradation in the brightness was observed, and good displaycharacteristics were obtained.

Example 12

A simple-matrix color organic electroluminescent device was prepared inthe same manner as in Example 9, except that the varnish G prepared inExample 7 was used and the curing was performed at 230° C. for 30minutes. When the resulting device was driven line-sequentially, nodegradation in the brightness was observed, and good displaycharacteristics were obtained.

Example 13

A photosensitive polyimide insulation layer was formed on the firstelectrode on the substrate in the same manner as in Example 9, exceptthat the curing was performed by heating in an air atmosphere in an ovenat 180° C. for 30 minutes and the thickness of the insulation layer wasmade 3 μm. It was confirmed that the volume resistivity was at least5×10¹⁰ Ωcm. The cross-section of the border area of the insulation layerhad a forward tapered shape. The cone angle was approximately 45°.

An organic electroluminescent device was prepared using the substrateprovided with the insulation layer. The glass substrate provided withthe insulation layer was subjected to an oxygen plasma process or UVirradiation. Thereafter, a hole injection material or a holetransportation material dissolved in alcohol was applied on thesubstrate by spin coating to form a film. The resulting film was heatedin an oven at 180° C. for 30 minutes.

A pattern was formed at openings using red, blue, and green organicluminescent materials, which had been dissolved in toluene, by an inkjetmethod. The substrate was heated in an oven at 80° C. for 30 minutes.Finally, a second electrode was formed in the same manner as in Example9 and sealing was performed.

The resulting simple-matrix color organic electroluminescent device wascomposed of: the striped first electrode composed of ITO comprising 816strips at a pitch of 100 μm each having a width of 80 μm; patternedgreen, red, and blue luminescent layers arranged on the first electrode;and the striped second electrode comprising 200 strips at a pitch of 300μm each having a width of 250 μm and was orthogonal to the firstelectrode. Since three luminescent regions in red, green, and blueconstituted one pixel, the electroluminescent device of the presentinvention had 272×200 pixels at a pitch of 300 μm. Since the portions ofthe first electrode exposed by the insulation layer exclusively emittedlight, one luminescent region had a rectangular shape with a width of 70μm and a length of 250 μm.

When this device was driven line-sequentially, good displaycharacteristics were obtained. Because the edge portions of the firstelectrode were covered with the insulation layer, no short-circuitingdue to the field concentration was observed. Also, because thecross-section had the forward tapered shape, neither the thin-film layernor the second electrode suffered from thinning and stepped cuts at theborder portions of the insulation layer, and they were smoothlydeposited. Thus, no degradation in the brightness was observed insidethe luminescent region, and stable light emission was achieved. As thedurability test, the device was held at 85° C. for 250 hours, and theluminescent characteristics were then evaluated. The luminescent regiondid not diminish compared to the initial stage, and good luminescencewas obtained.

Example 14

An ITO electrode (pixels) of a predetermined pattern was formed on aplanarizing film of a substrate, i.e., a TFT substrate, comprisingswitching elements in such a manner that the ITO electrode was incontact with the source/drain electrodes on the substrate.

Using this substrate, an insulation layer, a hole injection or transportmaterial, an electroluminescent material, and a second electrode wereformed on the substrate, and the resulting substrate was sealed as inExample 13.

When this device was driven in an active matrix mode, good displaycharacteristics were obtained. Because the edge portions of the firstelectrode were covered with the insulation layer, no short-circuitingdue to the field concentration was observed. Moreover, because thecross-section had the forward tapered shape, neither the thin-film layernor the second electrode suffered from thinning and stepped cuts at theborder portions of the insulation layer, and they were smoothlydeposited. Thus, no degradation in the brightness was observed insidethe luminescent region, and stable light emission was achieved. As thedurability test, the device was held at 85° C. for 250 hours, and theluminescent characteristics were then evaluated. The luminescent regiondid not diminish compared to the initial period, and good luminescencewas obtained.

Example 15

In a dry nitrogen gas stream, 11.41 g (0.057 mol) of4,4′-diaminodiphenyl ether, 1.24 g (0.005 mol) of1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 8.18 g (0.075 mol) of3-aminophenol (Tokyo Kasei Kogyo Co., Ltd.) as an endcap agent weredissolved in 80 g of NMP. Bis(3,4-dicarboxyphenyl)ether dianhydride(31.02 g, 0.10 mol) and 20 g of NMP were added thereto, and the mixturewas allowed to react at 20° C. for 1 hour and then at 50° C. for 4hours. Thereafter, 15.19 g (0.127 mol) of N,N-dimethylformamide dimethylacetal was diluted with 4 g of NMP, and the resulting dilution was addeddropwise over the period of 10 minutes. After the dropwise addition, themixture was agitated at 50° C. for 3 hours. After the completion ofagitation, the solution was poured into 2 l of water, and deposits ofpolymer solid were collected by filtration. The collected deposits werewashed three times with water and dried in a vacuum dryer at 80° C. for20 hours. The resulting polymer solid was subjected to infraredabsorption spectrum measurement, and the absorption peaks of thepolyimide imide structure were not detected at around 1780 cm⁻¹ and 1377cm⁻¹. Subsequently, 8.5 g of this polymer solid was mixed with 1.5 g ofthe polymer solid obtained in Example 1, and the rate of imideconversion of the polymer solid mixture thus obtained was inspected.

Subsequently, 10 g of the polymer solid mixture, 0.5 g of aphotopolymerization initiator, i.e., bis(α-isonitrosopropiophenoneoxime)isophthal, 1 g of a thermally crosslinkable compound NikalacMX-270 (trade name, Sanwa Chemical Co., Ltd.), 2 g of Tris P-Pa, and 5 gof trimethylolpropane diacrylate (a compound having a polymerizablefunctional group comprising unsaturated double bonds) were dissolved in12 g of ethyl lactate to prepare a varnish J, which is anegative-working photosensitive polyimide composition. With the use ofthis varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 170° C. for 60 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Example 16

In a dry nitrogen gas stream, 30.03 g (0.082 mol) of2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 1.24 g (0.005mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2.73 g (0.025mol) of 3-aminophenol (Tokyo Kasei Kogyo Co., Ltd.) as an endcap agentwere dissolved in 100 g of NMP. To this solution, 31.02 g (0.10 mol) ofbis(3,4-dicarboxyphenyl)ether dianhydride and 30 g of NMP were added,and the mixture was allowed to react at 20° C. for 1 hour and then at50° C. for 4 hours. Thereafter, 15.19 g (0.127 mol) ofN,N-dimethylformamide dimethyl acetal was diluted with 4 g of NMP, andthe resulting dilution was added dropwise over the period of 10 minutes.After the dropwise addition, the mixture was agitated at 50° C. for 3hours. After the completion of agitation, the solution was poured into 2l of water, and deposits of polymer solid were collected by filtration.The collected deposits were washed three times with water and dried in avacuum dryer at 80° C. for 20 hours. The resulting polymer solid wassubjected to infrared absorption spectrum measurement, and theabsorption peaks of the polyimide imide structure were not detected ataround 1780 cm⁻¹ and 1377 cm⁻¹. Subsequently, 5 g of this polymer solidwas mixed with 5 g of the polymer solid obtained in Example 5, and therate of imide conversion of the polymer solid mixture thus obtained wasinspected.

Subsequently, 10 g of the polymer solid mixture, 0.4 g of aphotopolymerization initiator, i.e.,1,2-octanedione,1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime), 1.5 g ofa thermally crosslinkable compound Nikalac MW-100 LM (trade name, SanwaChemical Co., Ltd.), 0.3 g of an A-DMA colorant (trade name, HodogayaChemical Co., Ltd.), and 10 g of trimethylolpropane triacrylate (acompound having a polymerizable functional group comprising unsaturateddouble bonds) were dissolved in 10 g of diacetone alcohol to prepare avarnish K, which is a negative-working photosensitive polyimidecomposition. With the use of this varnish, a photosensitive polyimidefilm was formed on a silicon wafer as described above, exposed,post-exposure baked, developed in an alkaline developer, and then heattreated at 180° C. for 60 minutes. The alkaline developability of thevarnish, the film retentivity, the film retentivity after shrinkage, thecrack resistance, and stress resistance were evaluated.

Example 17

In a dry nitrogen gas stream, 30.03 g (0.082 mol) of2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), 1.24 g (0.005mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2.73 g (0.025mol) of 3-aminophenol (Tokyo Kasei Kogyo Co., Ltd.) as an endcap agentwere dissolved in 100 g of NMP. To this solution, 31.02 g (0.10 mol) ofbis(3,4-dicarboxyphenyl)ether dianhydride and 30 g of NMP were added,and the mixture was allowed to react at 20° C. for 1 hour and then at50° C. for 4 hours. Thereafter, 15.19 g (0.127 mol) ofN,N-dimethylformamide dimethyl acetal was diluted with 4 g of NMP, andthe resulting dilution was added dropwise over the period of 10 minutes.After the dropwise addition, the mixture was agitated at 80° C. for 7hours. After the completion of agitation, the solution was poured into 2l of water, and deposits of polymer solid were collected by filtration.The collected deposits were washed three times with water and dried in avacuum dryer at 80° C. for 20 hours. The resulting polymer solid wassubjected to infrared absorption spectrum measurement, and theabsorption peaks of the polyimide imide structure were not detected ataround 1780 cm⁻¹ and 1377 cm⁻¹. Subsequently, 7 g of this polymer solidwas mixed with 3 g of the polymer solid obtained in Example 5, and therate of imide conversion of the polymer solid mixture thus obtained wasinspected.

Subsequently, a varnish L, which is a negative-working photosensitivepolyimide composition, was prepared in the same manner as in Example 16,except for the use of 10 g of the polymer solid mixture. With the use ofthis varnish, a photosensitive polyimide film was formed on a siliconwafer as described above, exposed, post-exposure baked, developed in analkaline developer, and then heat treated at 180° C. for 60 minutes. Thealkaline developability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Comparative Example 1

In a dry nitrogen gas stream, 11.41 g (0.057 mol) of4,4′-diaminodiphenyl ether, 1.24 g (0.005 mol) of1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 8.18 g (0.075 mol) of3-aminophenol (Tokyo Kasei Kogyo Co., Ltd.) as an endcap agent weredissolved in 80 g of NMP. To this solution, 31.02 g (0.10 mol) ofbis(3,4-dicarboxyphenyl)ether dianhydride and 20 g of NMP were added,and the mixture was allowed to react at 20° C. for 1 hour and then at50° C. for 4 hours. Thereafter, 15.19 g (0.127 mol) ofN,N-dimethylformamide dimethyl acetal was diluted with 4 g of NMP, andthe resulting dilution was added dropwise over the period of 10 minutes.After the dropwise addition, the mixture was agitated at 50° C. for 3hours. After the completion of agitation, the solution was poured into 2l of water, and deposits of polymer solid were collected by filtration.The collected deposits were washed three times with water and dried in avacuum dryer at 80° C. for 20 hours. The resulting polymer solid wassubjected to infrared absorption spectrum measurement, and theabsorption peaks of the polyimide imide structure were not detected ataround 1780 cm⁻¹ and 1377 cm⁻¹. A polyimide precursor polymer solid (10g) thus obtained, 0.5 g of a photopolymerization initiator, i.e.,bis(α-isonitrosopropiophenone oxime)isophthal, 1 g of a thermallycrosslinkable compound Nikalac MX-270 (trade name, Sanwa Chemical Co.,Ltd.), 2 g of Tris P-Pa, and 5 g of trimethylolpropane diacrylate (acompound having a polymerizable functional group comprising unsaturateddouble bonds) were dissolved in 12 g of ethyl lactate to prepare avarnish A1, which is a negative-working photosensitive polyimideprecursor composition. With the use of this varnish, a photosensitivepolyimide precursor film was formed on a silicon wafer as describedabove, exposed, post-exposure baked, developed in an alkaline developer,and then heat treated at 170° C. for 60 minutes. The alkalinedevelopability of the varnish, the film retentivity, the filmretentivity after shrinkage, the crack resistance, and stress resistancewere evaluated.

Comparative Example 2

In a dry nitrogen gas stream, 46.55 g (0.077 mol) of thehydroxyl-group-containing diamine compound (III), which was obtained inSynthetic Example 3, was dissolved in 250 g of NMP. Thehydroxyl-group-containing acid anhydride (b) (71.45 g, 0.1 mol), whichwas obtained in Synthetic Example 2, and 7.38 g (0.045 mol) of3-hydroxyphthalic anhydride (Tokyo Kasei Kogyo Co., Ltd.) as an endcapagent were added thereto, and the mixture was allowed to react at 60° C.for 2 hours. Thereafter, 15.19 g (0.127 mol) of N,N-dimethylformamidedimethyl acetal was diluted with 4 g of NMP, and the resulting dilutionwas added dropwise over the period of 10 minutes. After the dropwiseaddition, the mixture was agitated at 50° C. for 3 hours. After thecompletion of agitation, the solution was poured into 2 l of water, anddeposits of polymer solid were collected by filtration. The collecteddeposits were washed three times with water and dried in a vacuum dryerat 80° C. for 20 hours. The resulting polymer solid was subjected toinfrared absorption spectrum measurement, and the absorption peaks ofthe polyimide imide structure were not detected at around 1780 cm⁻¹ and1377 cm⁻¹. A polyimide precursor polymer solid (10 g) thus obtained, 2.5g of a photopolymerization initiator, i.e.,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 8 g ofpentaerythritol triacrylate (a compound having a polymerizablefunctional group comprising unsaturated double bonds), 5 g of athermally crosslinkable compound DML-PC (trade name, Honshu ChemicalIndustry Co., Ltd.), and 1 g of vinyltrimethoxysilane were dissolved in10 g of 3-methyl-3-methoxybutanol to prepare a varnish B1, which is aphotosensitive polyimide precursor composition. With the use of thisvarnish, a photosensitive polyimide precursor film was formed on asilicon wafer as described above, exposed, post-exposure baked,developed in an alkaline developer, and then heat treated at 180° C. for60 minutes. The alkaline developability of the varnish, the filmretentivity, the film retentivity after shrinkage, the crack resistance,and stress resistance were evaluated.

Comparative Example 3

With the use of the varnish BI, which is a negative-workingphotosensitive polyimide precursor composition obtained in ComparativeExample 2, a photosensitive polyimide precursor film was formed on asilicon wafer as described above, exposed, post-exposure baked,developed in an alkaline developer, and then heat treated at 350° C. for60 minutes. The alkaline developability of the varnish, the filmretentivity, the film retentivity after shrinkage, the crack resistance,and stress resistance were evaluated.

Comparative Example 4

A varnish C1, which is a negative-working photosensitive polyimidecomposition, was prepared in the same manner as in Example 1, exceptthat 3-aminophenol was not used as an endcap agent. With the use of theresulting varnish, a photosensitive polyimide film was formed on asilicon wafer as described above, exposed, post-exposure baked,developed in an alkaline developer, and then heat treated at 170° C. for60 minutes. The alkaline developability of the varnish, the filmretentivity, the film retentivity after shrinkage, the crack resistance,and stress resistance were evaluated.

Comparative Example 5

A varnish D1, which is a negative-working photosensitive polyimidecomposition, was prepared in the same manner as in Example 2, exceptthat the amount of the hydroxyl-group-containing diamine compound (III)obtained in Synthetic Example 3 to be added was altered to 60.45 g (0.1mol) and the activated ester compound (I) was not used as an endcapagent. With the use of the resulting varnish, a photosensitive polyimidefilm was formed on a silicon wafer as described above, exposed,post-exposure baked, developed in an alkaline developer, and then heattreated at 200° C. for 60 minutes. The alkaline developability of thevarnish, the film retentivity, the film retentivity after shrinkage, thecrack resistance, and stress resistance were evaluated.

Comparative Example 6

A simple-matrix color organic electroluminescent device was prepared inthe same manner as in Example 9, except for the use of the varnish A1prepared in Comparative Example 1. When the resulting device was drivenline-sequentially, no degradation in the brightness was observed.However, a significant level of uneven luminescence was observed in theedge portion of the luminescent display unit, and good displaycharacteristics were not obtained.

Comparative Example 7

An onium salt (0.5 g, DPI-TF: trade name, Toyo Gosei Co., Ltd.) wasdissolved in the polyimide varnish C obtained in Example 3 to prepare avarnish E1. A simple-matrix color organic electroluminescent device wasprepared in the same manner as in Example 9, except that the varnish E1was used and heat treatment was carried out at 180° C. for 30 minutes.When the resulting device was driven line-sequentially, degradation inthe brightness was observed, and a significant level of unevenluminescence was observed in the edge portion of the luminescent displayunit. Good display characteristics were not obtained.

Compositions of Examples 1 to 8 and 15 to 17 are shown in Table 1,compositions of Comparative Examples 1 to 5 are shown in Table 2, andthe results of evaluation are shown in Table 3. TABLE 1 Resin Polymer(a) Compound (b) having a composition Polymer type Endcap agentpolymerizable group Photopolymerization initiator (c) Ex. 1 A 100% byweight of polyimide 3-Aminophenol TrimethylolpropaneBis(α-isonitrosopropiophenone diacrylate oxime)isophthal Ex. 2 B 100% byweight of polyimide Activated ester (I) Pentaerythritol2-Benzyl-2-dimethylamino-1-(4- triacrylate morpholinophenyl)-butanone-1Ex. 3 C 100% by weight of polyimide 3-Hydroxyphthalic Pentaerythritol2-Benzyl-2-dimethylamino-1-(4- anhydride triacrylatemorpholinophenyl)-butanone-1 Ex. 4 D 100% by weight of polyimide4-Aminothiophenol Dimethylol-tricyclodecane N-Phenylglycine diacrylateBis(α-isonitrosopropiophenone oxime)isophthal Ex. 5 E 100% by weight ofpolyimide 3-Aminophenol Trimethylolpropane1,2-Octanedione,1-[4-(phenylthio)- triacrylate phenyl]-,2-(o-benzoyloxime) Ex. 6 F 100% by weight of polyimide 3-HydroxyphthalicDimethylol-tricyclodecane 2-Benzyl-2-dimethylamino-1-(4- anhydridediacrylate morpholinophenyl)-butanone-1 Trimethylolpropane diacrylateEx. 7 G 100% by weight of polyimide 4-AminothiophenolN-(3-Diethylaminopropyl)- 1-Phenyl-1,2-butanedione-2-(o- methacrylamidemethoxycarbonyl)oxime Dimethylol-tricyclodecane diacrylate Ex. 8 H 100%by weight of polyimide 3-Aminophenol Dimethylol-tricyclodecane1-Phenyl-1,2-butanedione-2-(o- diacrylate methoxycarbonyl)oxime N-vinylcaprolactam Ex. 15 J 15% by weight of polyimide 3-AminophenolTrimethylolpropane Bis(α-isonitrosopropiophenone and 85% by weight ofdiacrylate oxime)isophthal polyimide precursor Ex. 16 K 50% by weight ofpolyimide 3-Aminophenol Trimethylolpropane 1,2-Octanedione,1-[4- and 50%by weight of triacrylate (phenylthio)phenyl]-,2- polyimide precursor(o-benzoyl oxime) Ex. 17 L 30% by weight of polyimide 3-AminophenolTrimethylolpropane 1,2-Octanedione,1-[4-(phenylthio)- and 70% by weightof triacrylate phenyl]-,2-(o-benzoyl oxime) polyimide precursorThermally Compound having Resin crosslinkable a phenolic compositioncompound (d) Colorant (e) hydroxyl group Solvent Ex. 1 A Nikalac MX-270None TrisP-PA Ethyl lactate Ex. 2 B None None None γ-Butyrolactone Ex. 3C DML-PC None None 3-Methyl-3-methoxybutanol Ex. 4 D TML-HQ None NonePropylene glycol monomethyl ether Ex. 5 E Nikalac MW-100LM A-DMA NoneDiacetone alcohol Ex. 6 F None Oil Blue 2N None Ethyl lactate CVL Ex. 7G DMOM-PTBP None BIR-PC γ-Butyrolactone Cyclopentanone Ex. 8 H B-a typebenzoxazine None BIR-PC Diacetone alcohol Ex. 15 J Nikalac MX-270 NoneTrisP-PA Ethyl lactate Ex. 16 K Nikalac MW-100LM A-DMA None Diacetonealcohol Ex. 17 L Nikalac MW-100LM A-DMA None Diacetone alcohol

TABLE 1 Resin Polymer (a) Compound (b) having composition Polymer typeEndcap agent a polymerizable group Photopolymerization initiator (c)Comp. Ex. 1 A1 100% by weight of 3-Aminophenol TrimethylolpropaneBis(α-isonitrosopropiophenone polyimide precursor diacrylateoxime)isophthal Comp. Ex. 2 B1 100% by weight of 3-HydroxyphthalicPentaerythritol 2-Benzyl-2-dimethylamino-1-(4- polyimide precursoranhydride triacrylate morpholinophenyl)-butanone-1 Comp. Ex. 3 B1 100%by weight of 3-Hydroxyphthalic Pentaerythritol2-Benzyl-2-dimethylamino-1-(4- polyimide precursor anhydride triacrylatemorpholinophenyl)-butanone-1 Comp. Ex. 4 C1 100% by weight of NoneTrimethylolpropane Bis(α-isonitrosopropiophenone polyimide diacrylateoxime)isophthal Comp. Ex. 5 D1 100% by weight of None Pentaerythritol2-Benzyl-2-dimethylamino-1-(4- polyimide triacrylatemorpholinophenyl)-butanone-1 Thermally Compound having a Resincrosslinkable phenolic hydroxyl composition compound (d) Colorant (e)group Solvent Comp. Ex. 1 A1 Nikalac MX-270 None TrisP-PA Ethyl lactateComp. Ex. 2 B1 DML-PC None None 3-Methyl-3-methoxybutanol Comp. Ex. 3 B1DML-PC None None 3-Methyl-3-methoxybutanol Comp. Ex. 4 C1 Nikalac MX-270None TrisP-PA Ethyl lactate Comp. Ex. 5 D1 None None Noneγ-Butyrolactone

TABLE 3 Polymer (a) Resin Rate of imide Heat treatment compositionPolymer type Endcap agent conversion (%) conditions Ex. 1 A Polyimide3-Aminophenol 100 170° C. × 60 min. Ex. 2 B Polyimide Activated ester(a) 100 200° C. × 60 min. Ex. 3 C Polyimide 3-Hydroxyphthalic 100 180°C. × 60 min. anhydride Ex. 4 D Polyimide 4-Aminothiophenol 100 150° C. ×60 min. Ex. 5 E Polyimide 3-Aminophenol 100 180° C. × 60 min. Ex. 6 FPolyimide 3-Hydroxyphthalic 100 200° C. × 60 min. anhydride Ex. 7 GPolyimide 4-Aminothiophenol 100 210° C. × 30 min. Ex. 8 H Polyimide3-Aminophenol 100 180° C. × 30 min. Ex. 15 J Polyimide precursor/3-Aminophenol 20 170° C. × 60 min. polyimide Ex. 16 K Polyimideprecursor/ 3-Aminophenol 55 180° C. × 60 min. polyimide Ex. 17 LPolyimide precursor/ 3-Aminophenol 35 180° C. × 60 min. polyimide Comp.Ex. 1 A1 Polyimide precursor 3-Aminophenol 0 170° C. × 60 min. Comp. Ex.2 B1 Polyimide precursor 3-Hydroxyphthalic 0 180° C. × 60 min. anhydrideComp. Ex. 3 B1 Polyimide precursor 3-Hydroxyphthalic 0 350° C. × 60 min.anhydride Comp. Ex. 4 C1 Polyimide None 100 170° C. × 60 min. Comp. Ex.5 D1 Polyimide None 100 200° C. × 60 min. Film Film retentivity ResinDevelopability in retentivity after shrinkage Crack Stress compositionalkaline solution (%) (%) resistance resistance Ex. 1 A Soluble inalkaline 90 92 Not cracked Not wrinkled developer Ex. 2 B Soluble inalkaline 88 88 Not cracked Not wrinkled developer Ex. 3 C Soluble inalkaline 90 91 Not cracked Not wrinkled developer Ex. 4 D Soluble inalkaline 92 93 Not cracked Not wrinkled developer Ex. 5 E Soluble inalkaline 91 93 Not cracked Not wrinkled developer Ex. 6 F Soluble inalkaline 92 87 Not cracked Not wrinkled developer Ex. 7 G Soluble inalkaline 91 90 Not cracked Not wrinkled developer Ex. 8 H Soluble inalkaline 92 90 Not cracked Not wrinkled developer Ex. 15 J Soluble inalkaline 88 83 Not cracked Not wrinkled developer Ex. 16 K Soluble inalkaline 90 87 Not cracked Not wrinkled developer Ex. 17 L Soluble inalkaline 88 85 Not cracked Not wrinkled developer Comp. Ex. 1 A1 Solublein alkaline 85 78 Cracked Wrinkled developer Comp. Ex. 2 B1 Soluble inalkaline 83 78 Cracked Wrinkled developer Comp. Ex. 3 B1 Soluble inalkaline 84 70 Not cracked Wrinkled developer Comp. Ex. 4 C1 Insolublein alkaline 100 91 — — developer Comp. Ex. 5 D1 Insoluble in alkaline100 86 — — developer

All publications, patents, and patent applications cited herein areincorporated herein by reference in their entirety.

INDUSTRIAL APPLICABILITY

The present invention relates to a heat resistant resin composition thatis suitable for a surface protective film of a semiconductor device, aninterlayer insulation film of a semiconductor device, an insulationlayer of an organic electroluminescent element, and an insulation filmfor protecting wirings of a circuit substrate.

1. A photosensitive resin composition comprising: (a) apolyimide-containing component comprising at least one group selectedfrom the group consisting of a carboxyl group, a phenolic hydroxylgroup, a sulfonic acid group, and a thiol group at the terminus of thepolymer main chain; (b) a compound having a polymerizable functionalgroup comprising unsaturated double and/or triple bonds; and (c) aphotopolymerization initiator.
 2. The photosensitive resin compositionaccording to claim 1, further comprising a thermally crosslinkablecompound.
 3. The photosensitive resin composition according to claim 1,further comprising a colorant.
 4. The photosensitive resin compositionaccording to claim 1, wherein the polyimide-containing componentcomprises at least one member comprising a structural unit representedby formula (1), formula (2), formula (3) or formula (4), and thepolyimide content is 10% by weight or more based on the amount of theentire polymer in the composition:

wherein R¹ represents a 4- to 14-valent organic group; R² represents a2- to 12-valent organic group; R³ and R⁵ each represent a hydrogen atomor an organic group having at least one member selected from the groupconsisting of a phenolic hydroxyl group, a sulfonic acid group, a thiolgroup, and organic groups having 1 to 20 carbon atoms, which may be thesame or different; R⁴ represents a 2-valent organic group; X and Y eachrepresent a 2-valent to 8-valent organic group having at least onemember selected from the group consisting of a carboxyl group, aphenolic hydroxyl group, a sulfonic acid group, and a thiol group; n isa number between 3 and 200; and m, α, and β are each an integer between0 and
 10. 5. The photosensitive resin composition according to claim 4,wherein m in formulae (1) to (4) is
 0. 6. The photosensitive resincomposition according to claim 2, wherein the thermally crosslinkablecompound comprises an organic group represented by formula (5):

CH₂—R⁶)  (5) wherein R⁶ represents a hydrogen atom, an alkyl grouphaving 1 to 20 carbon atoms, a alicyclic group having 4 to 20 carbonatoms, or an R⁷CO group; and R⁷ represents an alkyl group having 1 to 20carbon atoms.
 7. The photosensitive resin composition according to claim2, wherein the thermally crosslinkable compound comprises a benzoxazinecompound.
 8. A process for producing a heat resistant resin comprisingapplying the photosensitive resin composition according to claim 1 to asupport substrate to form a coating; and developing the coating using adeveloper to produce the heat resistant resin.
 9. An electroniccomponent comprising the heat resistant resin obtained by the methodaccording to claim 8 as a surface protecting film or an interlayerinsulation film.
 10. A method for producing an organicelectroluminescent device comprising forming a photosensitive resin filmby applying the photosensitive resin composition according to claim 1 toa substrate having a first electrode formed thereon; forming aninsulation layer by developing the photosensitive resin film; forming aluminescent layer, and forming a second electrode.
 11. A display unitcomprising the heat resistant resin film obtained by the methodaccording to claim 8.